Lubricant



Patented Nov. 29, 1949 Biivid; n; Ad'elsorr; BerkeleyLaiiji, th to Shell Development. Company, San Francisco" Gal-iii, a corporation of De ay ii in drawing. Application Maren- 31, ism, Serial No. 738,495 e,

This: invention relates to novel reaction products having properties of greatly improving and stabilizing lubricants, and is a continuation-inpart of my pending application, Serial No. 718,617, filed December 26, 1946. This invention also pertains to lubricants, such as mineral lubricating oils,- synthetic lubricants of hydrocarbon or non-hydrocarbon origin, and the like, containing therein a multi-functional additive having detergent and anti-ringsticking, properties, as well as acting as an inhibitor of oxidation and corrosion.

It is well known that various lubricants whether doped or undopedteiid to oxidize and to form corrosive bodies and sludge, when used in modern engines and machines operating under ordinary conditions orat high speeds elevated temperatures, heavy loads and/or other adverse condi= tions; Some of the deterioration products of 1u= bricants formed during, t eirs-Se are hard} car'- bonaceous materials which adhere to metal surfaces and causes sr'athing' and scuffing of movable metal parts and the sticking of valves and piston rings iii engines. In. addition, presently known lubricants are generally incapable of maintaining av continuous lubricating film between movable metal parts, resulting in gradual or rapid wearing away of metal parts. The darnage thus caused required replacement of such parts or even the complete overhauling 'f'engins and machines, resulting in expensive loss of production and time.

In the case of the highest quality noncbrrc ive, stable lubricating oils, which have been highly refined for specific uses, or synthetic; lubricants 20 Claims. (01. resin-46 t) To improve the lubricating properties: of tin and synthetic lubricants it has become the pra= tice to blend with various lubricants, one arid" in most cases more than one addition agents, additives have the effect or property of inhibiting deterioration of lubricants and impart to them iaefwitn th aid of n at ve apel/estate also been ,dilqp wh o s m ra i y of modif'iingtthev carbonaceous materials formed,

deter ion of lubricants, on pistpn rods,

rings anc valves, and. other metal parts in inter;-

combustion engines, automotive and truck engines, attests eng nes, high speed Diesel, engiiisaiid' the like. fs'u' n additives serve a very important fiifitioril becaus liy mannin is carbonaceous material st) that'it can be removed l additives sw ete developed for. the purpose of acting as-detergents in lubricants, in

order to assistin tljie ren oval of soot or sludge, varnish, lacquer formed. from deterioration, of the ,oil when subjected to high operating temperatures. Detergents due to their cleaning action firvent tli build up of these deleteriousmaterials andassistin removing those formed; 1 Anti-wear additives have the; property of reducing. friction of movable-metal; parts of the same or different metals}. Due to thefunction exerted or property imparted, by such: additives on lubricants; Wear caused by direct frictional contact of metals: can be greatly reduced. Also additives have been developect'to withstand extreme pressures; disperse impurities, solubilize certain additives and the like.

c The development of numerous additives has been due-ta thefattliat most, if not all additives are capable of functioning in substantially only one specific manner. Very few lubricant additives have the ability of improving a lubricant in more than ust die, respect. Thus a good antioXida-ritmightr'iot be able to inhibit lacquer and varnish formation-on piston rods or act as a detergent or corrosion inhibitor. In many cases it is found that tit! waists sessesses very good properties. in one respect, but is the cause of harmful formations and thereforedetrimental as an additive another respect. Therefore, other additives are frequently required to obtain a good stable lubricant Thecombination of additives iii liitricaiits' additive exerts its influence without interfering with the function of other additives is a difficult matter. to attain. In most cases additives co-r'eact or interfere with eachio'ther. To prevent thi great care must be taken selecting the add'iti mixing them in specific proportions and: continuously watching and i'iila-Eing additives which have stopped functioningor have deteriorated.

synthetic lubricants and the like, a multi-func tional material so as to inhibit oxidation and corrosion and prevent the formation of sludge, varnish and lacquer in said lubricants even under adverse operating conditions. Still another object of this invention is to use in lubricating compositions a multi-functional material which prevents ringsticking as well as the sticking of other engine parts due to deterioration of the lubricant. Also it is an object of this invention to use in 'oleaginous materials, e. g. in lubricating compositions, a multi-functional material which inhibits wear, scufiing, scratching and other damage to engine parts. Furthermore it is an object of this invention to provide novel multi-functional improving and enhancing additives for lubricating bases. Other objects of this invention will appear as the description proceeds. 7

To the accomplishment of the foregoing and related ends, this invention consists of features which will be hereinafter, fully described, and particularly pointed out in the claims, the following description setting forth in detail certain embodiments of the invention, these being illustrative of but a few variations in which the principle of the invention may be employed.

Broadly stated, this invention is directed to the use, in lubricants, of reaction products obtained by reacting organic compounds with hydrogen sulfide in the presence of ammonium hydrosulfide and treating said reaction products with phosphorus and sulfur and/or a sulfur-containing agent, such as elemental sulfur, sulfur halides, sodium polysulfides, phosphorus sulfides, and the like. Among the organic compounds which can be used to form reaction productsof this invention are: r

I. ALIPHATIC HYnRocARBoNs Acycl ic compounds A. Saturated parafilnlc hydrocsrbons above 6 carbon atoms such as B. Unsaturated paraflinic hydrocarbons above 6 bon atoms such as fi unds of group HA and the III. CYCLIC 'IERPENES IV. HETEROCYCLIC COMPOUNDS cyrnene furan. furfural, limonone iuriuryl alcohol, pinene [urolc acid, I I bornylene pyrone, pyridine, methene picolinic acid, terpinolene nicotinic acid, terpin pyran, morpholine. menthol coumarono menthone and the like. lsoborneol camphor Both the cyclic terpenes and the heterocyclic compounds can have attached thereto substituent radicals, such as alkyl and alkenyl radicals, hydroxy and halogen groups, and the like.

V. ALCOHOLS A. Aliphatic (saturated and B. Aromatic alcohols: unsaturated): phenyl ethyl alcohol amyl alcohol phenyl octyl alcohol hexyl alcohol octadecyl bcnzyl alcohol heptyl alcohol benzyl alcohol octyl alcohol and the like. decyl alcohol 0. Cyclic alcohols: dodecyl alcohol naphthenic alcohol octadecyl alcohol carnaubyl alcohol oleyl alcohol Polyhycric aliphatic alcohols: monnitol glycols sorbltol pinocols and the like. erythrol D. Natural occurring alcohols and synthetic alcohols:

Alcohols as found in wool fat, sperm oil Alcohols produced by oxidation of hydrocarbons, c. g.

parafiin wax sweat wax petrolatum and the like.

v1. PI-lENOLIC COMPOUNDS Phenol, alkyl phenol, catechol, resorcinol, pyrogallol.

All of these compounds may contain substituent groups such as alkyl radicals, amino, halogen, carboxyl and the hire, hydroqulnone, quinone, orcinol, phloroglucinol, cresols, tbymol, seligenin, cinnaniyl alcohol, methyl phenyl carbinol, eugenol, cardanols, etc.

V11. ACIDS A. Aliphatic (mono and poly- B. aromatic acids:

alkyl malonic acid alkyl succinic acid alkyl glutaric acid glycolic acid pyruoic acid phthalonic acid lactic acid alkyl maleic acid alkyl malic acid alkyl tartaric acid alkyl citric acid keto acids subenc acid alkyladipic acid tartronic acid and the like, acids produced by oxidation of hydrocarbon, e. g. paraifin wax and the like.

Both the aromatic and aliphatic acids of group VII can have attached thereto substituent groups as suggested under groups II, III, and IV.

VIII. ESTERS Esters contemplated for use in this invention may be obtained by reactioning any of the compounds listed under group V and VI and their derivatives, with any of the acids listed under group VII. v

A. Aliphatic (saturated and B. Cyclic and poly ethers: unsaturated) ethylene oxide methyl, ethyl methyl, propylene oxide ethyl, ethyl propyl, acetal, dioxan' isopropyl, octyl, and the like.

ethers and the like; vinyl, allyl, crotonyl ethers and the like and mixture of saturated and unsaturated ethers.

C. Aromatic ethers: .D. Substituted ethers:

Specifically it is deanisole, phenetole, kyloxy others diphenyl, dixenyl, of polyhydroxy dinaphthyl ethers, aromatics such as benzyl phenyl ether, resorcinal, benzyl ether pyrogallol cardaoxyethanol and the like. and the like.

X. ALDEHYDES A. Aliphatic (saturated and B. Aromatic: unsaturated) Benzaldehyde acetaldehyde cinnamaldehyde propionaldehyde salicylaldehyde butyraldehyde naphthaldehyde caproaldehyde vanillin, etc. and the like; acrolein, crctonaldehyde, citral, etc.

XII. KETONES A. Aliphatic (saturated and B. Aromatic: unsaturated): acetoph enone acetone, butanone, hexanone, propiophenone oleone, palmitone, methyl ethyl dibenzyl ketone ketone, methyl propyl ketone, benzyl phenyl ketone butyrone, butenone, pentanone, benzophenone phorone, pentanedione, mesityl and the like. oxide, diethyl ketone, B-methylheptanone, di-isobutyl ketone, diacetone alcohol, and the like.

C. Cyclic ketones: pure isophorone 1 cyclobutanoue and isophorone bottoms the cyclopentanone manufacture of which will be quinones fully described hereinafter. cycloheptanone XII. NATURAL FATS, OILS AND WAXES THEIR DERIVATIVES AND MISCELLANE- OUS COMPOUNDS A. Vegetable and animal oils, fats, and waxes such as:

Wool fat castor 011 B. Petroleum hydrocarbons such as:

' naphtha kerosene mineral seal oil gas oils,'etc.

XIII. Metal salts and organic bases of organic acidic materials listed in any of the above groups, their mixtures, or various combinations may be treated with hydrogen sulfide in presence of ammonium hydrosulfide. Metal bases include those of the alkali metals, Cu, Mg, Ca, Cr, Br, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases include various nitrogen bases as primary, secondary, tertiary and quaternary amines.

Among the specific and preferred compounds contemplated for reacting with hydrogen sulfide in the presence of ammonium hydrosulfide and further treating said product with either a phosphorus sulfide and/or a sulfurizing agent, may be mentioned: stilbene, oleic acid, ammonium oleate, potassium oleate, ammonium undecylenate',

d scribed QlQW- Isophorone bottoms, are primarily high molecular weight unsaturated ketones having at least 1. and. referabl m re n 18 carbon atoms in the molecule. Iifhese products may be obtained b n ees tiq o aestqn in a caustic ol t n under elevated temperature and pressure. Spe cifically the product is obtainable by condensing acetone in a 30% to 60% caustic solution at a temperature ranging between about 130 and about 170 6., and under a pressure of from about 300' to about 500 poundsper square inch. The resultant product is subjected to distillation .to remove distillable ketones and other constituents and impurities. The product remaining in the still is preferably purified by filtration, solvent treatment, and comprises crude unsaturated cyclic ketones of high molecular weight, preferably referred to as crude isophorone bottoms. The term isophorone bottoms as reterred to herein is. usually a complex mixture. of high molecular Weight unsaturatedcyclic ketones containing at least 12 and preferably more than 18 carbon atoms in the molecule. 'Ijhe product thus formed is not to be confused with straight isophorone which is specifically 3,5,5-trimethyl ,cycloheXene-2-one-1, which is an unsaturated cyclic ketone containing only nine carbon atoms in the molecule. Isophorone bottoms produced. by condensation of acetone under conditions referred to above includes within its scope any and .all unsaturated cyclic ketones containing at least 12 and preferably more than 18 carbon atoms. and having generally the chemical structural configuration of isophorone as well as the chemical structural configuration resulting from its further condensation. 1

Crude isophorone bottoms can be fractionated and/or chemically treated and each fraction therefrom can in turn be treated with ammonium hydrosulfide-hydrogen sulfide and thereafter with phosphorus sulfide. and/or sulfur compounds at elevated temperatures to produce a compound containing both phosphorus and/or sulfur. Among the various fractions which can be obtainedfrom crude isophorone bottoms are topped, crude isophorone bottoms which contain at least 18 carbon atoms in the molecular and are" obtained after removal of distillate from crude isophorone bottoms to a still head temperature of 140 C. at 10 mm. mercury pressure. Another fraction of crude isophoronebottoms can be subjected to hydrolysis with dilute sodium hydroxide and the acetone and isophorone formed removed by distillation. The bottoms can then be filtered and purified and comprise essentially unsaturated cyclic ketones containing at least 12 and more carbon atoms in the molecule and are referred to as crude, hydrolyzed isophorone bottoms. This material can be subjected to distillation to split it into two fractions. The distilled hydrolyzed isophorone fraction has a boiling point of about 140} C. at 10mm. mercury pressure and consists of a mixture of unsaturated cyclic ketones containing between 15 to 18 carbon atoms in the molecule. The-residue is referred to as topped,

rated with hydrogen sulfide.

aisson 7 crude-hydrolyzed isophoi-orie bottoms'andis similar to topped crude" lsophorone bottoms. residue comprises essentially .unsaturatedcyclic ketones of at least "carbonatoms and higher in the molecule.'- Crude 'isophorone bottoms can be also subjected --to condensation over solid sodium hydroxide to yield two typesof resinous materials. The first'resinous'fraction'or soft resin has a viscosity'at 210 F. of about -26 centistokes and an average molecular weight of from 320 to 350. The heavier fraction or medium resin has a viscosity at 210 FQof. about 80 to 120 centistokes and an average molecular weight of from 370 to 390. I The unsaturated cyclic ketones can be hydrogenated to produce saturated cyclic ketones. All of the variou's saturated andunsaturated cyclic ketone fractions obtained in the manner described above can, inaccordance with one phase of this invention, be firs't reacted with hydrogen sulfide in the presence of ammonium hydrosulfide; and the reaction .product thus formed may then be further treated with a phosphorus sulfide and/or a sulfurizing agent to form desired final reaction products having outstanding properties as improving agents for lubricants. Among the phosphorus sulfide and/or sulfurizing agents whichcan be used to treat the initial reaction, namely the reaction of hydrogen sulfideammonium hydrosulfide and an organic compound are: Pass, P483, and/or elemental sulfur;

Sch, S2C12, sodium sulfide, sodium tetra-sulfide,

sodium pentasulfide, and the like.

. The products formed by the reaction of ammonium hydrosulfide-hydrogen sulfide-with organic compound can-be prepared at room or elevatedtemperatures-preferably in closed vessels. The use of elevated temperatures apparently only speeds up the reaction. However, the cost of fuel and special equipment outweighs this feature, anclit has been ordinarily found more advantageous to simply allow the ammonium hydrosulfide-hydrogen sulfide organic compound reactions to take place at room temperature in closed vessels for the necessary period of time, e. g. from one week to one month or more, depending upon the organic material being treated. Th final reaction product which is formed by treating the reaction products of ammonium hydrosulfide-hydrogen sulfide and an organic compound with any of the previously mentioned phosphorus sulfide and/or sulfurizing agents can be carried out at elevated temperatures of between about 100 C. and about 200 C. and preferably between about 150 C. and about 170 C., and V if desired in the presence of a suitable inert solvent.

- To more clearly illustrate the present invention, the following examples are presented. It

is to be understood however that various modifications can be resorted to without departing from the spirit of the invention. 7

EXAMPLE I A. Initial reaction product of hydrogen sulfide in the presence of ammonium hydrosulfide with topped, crude isophorone bottoms Isopropyl alcohol (700 cc.) contained in a a-liter, thick-walled suction flask, was saturated with dry ammonia followed by dry hydrogen sulfide. A solution of 238.5 grams of topped, crude isophorone bottoms in 350 cc. isopropyl alcohol was added and the resultin solution was satu- The side-neck and mouth of the flaskwere then-closed and the flask and washed with water.

was allowed to stand for a week with infrequent shaking. Upon opening the flask a partial vacuum was discovered. The reaction mixture was filtered to remove impurities and the isopropyl' alcohol was removed from the filtrate by evaporation. The residue was dissolved in 500 cc. of a non-aromatic hydrocarbon having a boiling range of between about 164 F. and 233 F. After removal of the solvent in a current of nitrogen gas on a steam bath, a very viscous sticky mass was obtained, said mass possessing a pleasant odor and exhibitin much less fiow at room temperature than did the starting materials. The product was oil-soluble and on analysis contained:

B. Final reaction product obtained by treating (A) with phosphorus pentasnlfide To approximately one hundred grams of the above initial reaction product about 50 grams of phosphorus sulfide were slowly added and the mixture was constantly stirred and heated for about 5 hours. The heating was done by initially maintaining the temperature at about 60 C. to C. and then rapidly heating to approximately C. and maintaining the reaction at this temperature until completed. At the end of the reaction period, the desired product was extracted with a non-aromatic hydrocarbon having a boiling range of between about 164 F. and 233 F. The solution was filtered and the filtrate evaporated at steam temperature in a current of carbon dioxide. The resultant product was a soft, brown solid which contained 14.2% sulfur and 4.6% phosphorus.

The process was repeated with initial reaction products as above but having sulfur contents of (a) 3.27 to 3.28% sulfur and (b) 4.20% to 4.30% sulfur and these final phosphorus sulfide-reaction products on analysis contained:

(2) Percent S in initial product (A) 4.2 to 4.3% S by wt. Percent S and P after treating initial product Pwith P2885- ercent 14.3 to 15 47 S b wt Percent P} final ream 910mm {421 to 4 (S P by wt EXAMPLE II A. Initial reaction product of ammonium hydrosulfide-hydrogen sulfide and topped, crude isophorone bottoms This reaction product was prepared in an isopropyl alcohol medium (1315 cc.) using about 295 gm. of topped, crude isophorone bottoms in an autoclave for 5 /2 hours at 96 C. to 101.5 C.

.75 The product was then treated as indicated in Per cent by wt. Nitrogen f; 03 (9) er t ths Wt Ox en a--, 6 M01. Wt 356 product as obtained under A with sulfur To approximately 80 gms. of the above initial rea otion'product about 16 gm. of elemental sulfur were added and the mixture was constantly stirred and heated for 2 hours at a temperature between about 150 to 170 C. The resultant product was a dark brown very viscous mass which contained about 16.8% sulfur by weight.

The process of sulfurizing the above initial reaction product was repeated as indicated under B, except that thereaction time was increased to 4 hours and on analysis this reaction product contained 17.1% sulfurbyweight.

Other phosphorus and sulfur and/or sulfur treated ammonium hydrosulfide-hydrogen sulfide-organic compound reaction products which are particularly preferable as lubricating oil ad: ditives are as follows:

(1) Ammonium hydrosulfide-hydrogen sulfidemesityl oxide treated with phosphorus pentasulfide and/or elemental sulfur.

(2) Ammonium hydrosulfide-hydrogen sulfidediacetone alcohol treated with phasev phorus pentasulfide and/or elemental sulfur.

Ammonium "hydrosulfide-hydrogen sulfidewax olefins treated with phosphorus pentasulfide and/or elemental sulfur and/or sodium tetrasulfide.

Ammonium hydrosulficle-hydrogen sulfidestilbene treated with phosphorus pentasulfide and/ or elemental sulfur.

Ammonium hydrosulfide-hydrogen sulfide? pentandione-2,4 treated with phosphorus pentasulfide and/or elemental sulfur and/or sodium tetrasulfide and/or sulfur chloride.

Ammonium hydrosulfide-hydrogen sulfidediphenyl methane treated with phos-. phorus pentasulfide and/or elemental sulfur.

Ammonium hydrosulfide-hydrogen sulfide? oleic acid treated with phosphorus pen-, tasulfide and/or elemental sulfur and/ s d t tre fifile- 3 Ammonium hydrosulfide hydrogen sulfideammonium oleate treated with phosphorus pentasulfide and/r elemental sulfur.

Ammonium hydrosulfideehydrogen sulfidepotassium oleatetreated with phospho:

rus pentasulfide and/or elemental 'sul-.,

fur.

Ammonium hydrosulfideehydrogen sulfideammonium undecylenate treated with phosphorus pentasulfide and/or elemental sulfur Ammonium hydrosulfide-hydrogen sulfideethyl undecylenate treated with phosphorus pentasulfide and/or elemental sulfur. I

A m v rq u fl le byq re en su fideethyl mmete treat wi h 1 9 19- rus pentasulfide and/or elemental sulfur.

10 Ammonium hydrosulfide-hydrogen sulfide:

methyl ricinoleate treated with phosphoru pentasulfide and/or elemental 51 E 1 7 Ammonium hydrosulfide-hydrogen sulfides. oottonseed oil treated with phosphorus pentasulfide and/or velemental sulfur. e lm ni m h dr s lfi dr de: r pe ed 011. t eat d t phosphorus penta ulfide and/or elemental sulfur. Ammo hy lr sulfide h d o ni sul de a .9i1t1fafi d.w t hos ho u ee:- tasulfide and/or elemental sulfur. Ammonium hydrosulfide-hydrogen sulfidedehydrated Castor oil treated with phosphorus pent'asulflde and/or elemental sulfur.. I Ammonium hydrosulfldeehydrogen sulfidetall oil treated with phosphorus pentasulfide and/or elemental sulfur. Ammonium hydrosulfide-hydrogen sulfide- Q nnamyl aleo e treated w th. B OSP Q' rus pentasulfide. and/or elemental sulfur. Ammonium hyd'rosulfide-hydrogen sulfidecinnamaldehyde treated with phospho, rus pentasulfide and/ or elemental sulfur.

TABLE I Oxidation stability determination [A refined undoped lubricating 011, 64-67 S. U. at 210 F. was employed, temperature 150. 0.]

Catalyst: 1 cm. (Bu/um. oil I Additives j" Amount per cent sulfate ash 1500 ml. oxygen, time 5 357 None 5.9 new; lmductbf E amp e I P rt namely, ammonium hydrosulfide hydrogen 's'ul fi d e wit upp d tie isophoro e bottoms 3 P treated reaction product'of ammonium :hyd;osultide-l y-v lrflse u fide w t t p crude isophorone bottom 4 Elemental sulfur treated re pi'oduct of'amnionium hyd s'ulfid'e hydrogn sulfide with' topped, crude isopl'lorono bottoms;." 5 Ga salt or alkyl pheri'olfo hyde condensation product... r '-F on petroleum sulfonate.' 6 Reaction Product oiExample 1 part A, namely. ammonium hydros'ulfide-hydr'ogen sulfide with topped, crude isophorone I bottoms 0. 1

4- Ca salt of alkyl phenoliormaldehyde condensation product la petroleum sulfon'ate 7 P 8 treated reaction product of ammonium hyd osuliide'hydrogen sulfldcwv th topp d, crude isophorone bottoms: rt. Ga s t f a kr Phenol-lormaldehyde condensation p llct -2 Ca petroleum sulfonate. 0. 1 8 Elemental sulfur treated reaction p roduct of ammonium hydrofi' l ydws n' su fi e w t topped, crude 'isoph'orone bot toms iie Salt o el yl eno orm'aldeh'yde condens ion product..- Ca petroleum sulfonate'i.

iai

A ll oxidation produots corrected to 15QU ml. oxygen absorbed per 1%(1 Loil, assuming amountjof product is proportioned to oxygen a so:

The doped and undoped oils were furthertested by a test known as the Thrust Bearing Corrosion test '(describedin the National Petroleum News, September'l'l, 1941, pp. R-294-296) which is carried out as follows: A hardened steel disc is made to rotate for 20 hours under constant pressure against three flat copper-lead bearings. The bearings assembly rests in a steel cup filled with the oil to be tested and the temperature of the oil is maintained at a predetermined figure by thermostatic control. The bearings are weighed before and after the test, the difference in weight representing the loss sustained during the test.

TABLE II Tests in thrust bearing corrosion machine [Fixed conditions CuPh bearings, 20 hours duration, 125 p. s. i. Thrust, 2,400 K. P. M. A refined, undoped, commercial lubricating oil 64*67 S. U. at 210 F. wase'mploycdl In addition to the above properties the addition of reaction products of this invention to mineral lubricating oils inhibits lacquer formation in engines operating under the most adverse conditions. Also reaction prodncts'of this invention can be used as valuable constituents of heavy duty oils, motor oils, Diesel oils, aviation oils, turbine oil, synthetic oils and the like because of their anti-corrosion, antioxidation, and antiwear properties. Besides their utility as lubricating oil additives, reactionproducts of this invention are useful as anti-oxidantsfor natural and, synthetic rubber and other organic materials which are subject to oxidation deterioration. The amount of additive used can be varied over wide limits but generally it is notneoessary to use more than by weight of the reaction product and preferably only between'about 0.1 to 2.0% by weight is added to base lubricants.

Because of its synergistic effect the reactio product of this invention can be combined with other additives in lubricants, such as, blooming agents, pour point depressants or viscosity improvers, extreme pressure agents, antifoaming agents and the like. Among the specific additives which can be usedare oil-soluble detergents which include oil-soluble salts of various bases with detergent forming acids. Such bases include metal as well as organic bases. Metallic bases include those of the alkali metals, Cu, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases include various nitrogen bases as primary, secondary, tertiary and quaternary amines.

Examples of detergent forming acids are the various fatty acids of, say, to 30 carbon atoms,

12 wool fat acids, paraflin wax acids (produced by oxidation of paraffin wax) chlorinated fatty acids, rosen acids, aromatic carboxylic acids including aromatic fatty acids, aromatic hydroxy fatty acids, paraiiin wax'benzoic acids, various alkyl salicylic acids, phthalic acid monoesters, aromatic keto acids, aromatic ether acids, diphenols as di- (alkyl-phenol) sulfides and disulfides, methylene bis alkylphenolsysulfonic acids such as may be produced by treatment of alkyl aryl hydrocarbons or high boiling petroleum oils with sulfuric acid; sulfuric acid mono-esters; phosphoric, arsonic and antimony acid mono and diesters, including the corresponding thio phosphoric, arsenic and antimony acids; phosphonic and arsonic acids and the like.'

Additional detergents are the alkaline earth phosphate diesters, including the thiophosphate diester; the alkaline earth diphenolates, specifically the calcium and barium salts of diphenol mono and poly sulfides. V

Non m'etallic detergents include compounds such as the phosphatides such as lecithin and cephlin, certain fatty oils as rapeseed oils, volto lized fatty or mineral oils and the like.

An excellent metallic detergent for the present purpose is the calcium salt of oil-soluble petroleum sulfonic acids. This may be present advantageously in the amount of about 0.025% to 0.2% sulfate ash. Also alkaline metal salts of alkyl phenol-aldehyde condensation reaction products are excellent detergents.

Antioxidants comprise several types, for example, alkyl phenols such as 2,4,6 trimethyl phenol, penta' methyl phenol, 2,4 dimethyl-6- tertiary-butyl phenol, 2,4 dimethyl 6 ootyl phenol, 2,6 di-tertiary-butyl-4-methyl-phen0l, 2,4,6 tritertiary-butyl phenol and the like; amino phenols as 'ben'zyl amino phenols; amines such as dibutyl-phenylene diamine, diphenyl amine, phenyl beta naphthylamine, phenyl alphanaphthylamine, dinaphthyl amine.

Corrosion inhibitors or anti-rusting compounds may also be present such as dicarboxylic acids of 16 and more carbon atoms; alkali metal and alkaline earth salts of sulfonic acids and fatty acids; organic compounds containing an acidic radical in close proximity to. a nitrile, nitro or nitroso group (e. g. alpha cyano stearic acid).

Extreme pressure agents which may be used "comprise: esters or phosphorus acids such as triaryl, alkyl hydroxy aryL'or aralkyl phosphates, thiophosphates or phosphites and the like; neutr'al aromatic sulfur compounds of relatively high boiling temperatures such as diaryl sulfides, 'diaryl disulfides, "alkyl aryl disulfides, e. g. diphenyl sulfide, diphenol sulfide, dicresol sulfide, dixylenol sulfide, methyl butyl diphenol sulfide, dibenzyl sulfide, corresponding diand tri-sul- 6U fides, and the like; sulfurized fatty oils or esters 'of fatty acids and monohydric alcohols, e. g.

urea or thiourea derivatives, e. g. urethanes,

allophanates, carbazides, carbazones, etc pol-ye isobutylene polymers, unsaturated polymerized esters of fatty acids and monohyd-ric alcohols-and The novel reaction products of this invention,

in addition to being excellent lubricating :oil i-m proving agents, are potent oxidation inhibitors for fuels, natural and synthetic rubber, wax coating compositions and other organic materials.

'It is to be understood that while the features of the invention have been described and illustrated in connection with certain specific-examples, the invention, however, is not to be limited thereto or otherwise restricted, except by the prior art and the scope of the appendedclaims.

I claim as my invention:

1. A lubricant comprising a major amount or a mineral lubricating oil and a minor amount, sui-ficient to stabilize said oil against oxidation and corrosion deterioration, of a reaction product obtained by first reacting an organic compound with hydrogen sulfide and ammonium hydrosulfide at room temperature and treating the resulting reaction .product with an inorganic compound selected from the group consisting of phosphorus sulfide, sulfur halide, elemental sulfur and alkali polysulfide at a temperature of at least 2. A lubricant comprising a major amount of mineral lubricating oil and a minor amount, sufficient to stabilize said oil against oxidation and corrosion deterioration, of a reaction product obtained by first reacting an organic compound with hydrogen sulfide and ammonium hydro-- product with an inorganic compound selected from the group consisting of phosphorus sulfide,

mon'ium hydrosulfide, at between about robin" temperature to about 100C. and treating the resulting reaction product with an inorganic compound selected from the group consisting of phosphorus sulfide, sulfur halide, elem'ei'ital sulfur and alkali polysulfide at a temperature of between about 150 to about 170 C.

4. A lubricant comprising a major amount of mineral lubricating oil and a minor amount, sulficient to stabilize said oil against oxidation and corrosion deterioration, of a reaction product obtained by first reacting a high molecular weight hydrocarbon with hydrogen sulfide and ammonium hydrosulfide, at between about room temperature to about 100 C. and treating the resulting reaction product with an inorganic compound selected from the group consisting of phosphorus sulfide, sulfur halide, elemental sulfur and alkali polysulfide at a temperature of between about 150 to about 170 C.

5,. A lubricant comprising a major of mineral lubricating oil and aminoramourit, 'suificient to stabilize said oi-l against oxidation and corrosion deterioration, or .a reaction product obtained by first reacting a saturated cyclic ketone having at least 12 carbon atoms with hydrogen sulfide and ammonium 'hydrosulfide, at between about room temperature to about C. and treating the resulting reaction product with an inorganic compoundsel'ected from the group consisting of phosphorus sulfide, sulfur halide, elemental sulfur and alkali polysulfide Eat a 'temperature of between about to about C.

6. A lubricant comprising a major amount of mineral lubricating 'oil and a minor amount, suilicient to stabilize said oil against oxidation and corrosion deterioration, of a reaction product'obtained by first reacting an unsaturated cyclic 'ketone having at least 12 carbon atoms with hydrogen sulfide and ammonium hydrosulfide, at between about room temperature to about 100 C. and treating the resulting reaction product with an inorganic compound selected from the group consisting of phosphorus sulfide, sulfur halide, elemental sulfur and alkali polysulfide at a temperature of between about 150 to about 170 C.

7. A lubricant comprising a major amount, of mineral lubricating oil and a minor amount, sumcieht to stabilize said 'oil against oxidation and corrosion deterioration, of a reaction product obtained by first reacting a wax olefin with hydrogen sulfide and ammonium hydrosulfide, at between about room temperature to about 100 C. and treating the resulting reaction product with an inorganic compound selected new the group consisting of phosphorus sulfide, sulfur halide, elemental sulfur and alkali polysulfide at a temperature of between about 150 to about 170 C.

'8. -A lubricant comprising "a major amount of mineral lubricating oil and a minor amount, of from 0.1% to 5% by weight, of a reaction product obtained by first reacting a saturated cyclic ketone having at -'least 12 carbon atoms with hydrogen sulfide and ammonium hydro'sulfide at between about room temperature and 100 C. and treating the resulting reaction product with phosphorus 'pentas'ulfide at a temperature of at least 150 'G.

0. A lubricant comprising 'a major amount of "mineral lubricating oil and a minor amount, of

from 0.1% to 51% by weightoi a reaction product obtained by first reacting an unsaturated cyclic ketone having at least '1 2-'carbon atoms with hydrogen sulfide and ammonium hydrosulfide'at between about room temperature and 100 C. "and treating the resulting reaction product with phosphorus pentasulfide "at a temperature of at least 150 ,C.

*10. A lubricant comprising a major amount of mineral lubricating *oil and a minor amount, of

from 0.1 to 5% by weight, of a reaction product obtained by first reacting awax olefin with hydrogen sulfide and ammonium 'hydrosulfide at between about room temperature and 100 C. and treating the resulting reaction product with phosphorus pentasulfide at a temperature of at least 150 C.

11. A lubricant comprising a major amount of mineral lubricating oil and a minor amount, of from 0.1% to 5% by weight, of a reaction product obtained by first reacting a saturated cyclic ketone having at least 12 carbon atoms with hydrogen sulfide and ammonium hydrosulfide at between about room temperature and 100 C. and

75 treating the resulting reaction product with ele- 15' mental sulfur at a temperature of at least 150 C. 12; A lubricant comprising a major amount of mineral lubricating oil and a minor amount, of

from 0.1% to by weight, of a reaction product obtained by first reacting an unsaturated cyclic ketone having at least 12 carbon atoms with hydrogen sulfide and ammonium hydrosulfide at between about room temperature and 100 C. and treating the resulting reaction'product with elemental sulfur at a temperature of at least 150 C.

13. A lubricant comprising a major amount of mineral lubricating oil and a minor amount. of from 0.1% to 5% by weight, of a reaction product obtained by first reacting a wax olefin withhydro'gen sulfide and ammonium hydrosulfide at between about room temperature and 100 C. and treating the resulting reaction product with elemental sulfur at a temperature of at least 150 C.

1 1. A'compounded'lubricant comprising a major amount of mineral lubricating oil and containing an active amount of calcium salt of alkyl phenol formaldehyde condensation reaction product, calcium salt of petroleum sulfonic acid as detergents, and a small amount of from 0.1% to 5% by weight of a reaction product obtained by first reacting an organic compound with hydrogen sulfide and ammonium hydrosulfide, at between about room temperature to about 100 C. and treating the resulting reaction product with an inorganic compound selected from the group consisting of phosphorus sulfide, sulfur, halide,

elemental sulfur and alkali polysulfide at a tern-1 perature of between about 150 to about 170 C.

15. Process of producing a stable, non-corrosive oil-soluble liquid hydrocarbon lubricant additive which comprises reacting in a solvent an organic compound with hydrogen sulfide and ammonium hydrosulfide at between about room temperature to about 100 C., and treating the resulting reaction product with phosphorus pentasulficle at between about 150 to 170 C. removing the solvent and adding from 0.1% to 5% of said final reaction product to a lubricant.

16. Process of producing a stable, non-corrosive oil-soluble liquid hydrocarbon lubricant additive which comprises reacting in a solvent an organic compound with hydrogen sulfide and ammonium hydrosulfide at between about room temperature to about 100 0., and treating the resulting reaction product with elemental sulfur at between about 150 to 170 C. removing the solvent and adding from 0.1% to 5% of said final fide in the presence of ammonium hydrosulfide,

at between about room temperature and about 1'6 C. and treating the resulting reaction product with an inorganic compound selected from the group consisting of phosphorus sulfide, sulfur halide, elemental sulfur and alkali polysulfide at a temperature of between about and'about 170 C., and thereafter neutralizing said reaction product to form the salt.

18. A lubricant comprising a major amount of mineral lubricating oil and a minor amount, suflicient to stabilize said oil against deteriora tion, of a salt of a reaction product obtained by first reacting a saturated cyclic ketone having at least 12 carbon atoms with hydrogen sulfideammonium hydrosulfide, at between about room temperature and about 100 C. and treating the resulting reaction product with an inorganic compound selected from the group consisting of phosphorus sulfide, sulfur halide, elemental sulfur and alkali polysulfide at a temperature of between about and about 0., and thereafter neutralizing said reaction product to form the salt.

19. A lubricant'comprising a major amount of mineral lubricating oil and a minor amount, sufv.ficient-to stabilize said oil against deterioration,

of a salt of a reaction product obtained by first reacting an'oxygen-containing organic compound with hydrogen sulfide-ammonium hydrosulfide, at between about room temperature and about 100 C. and treating the resulting reaction product with an inorganic compound selected from the group consisting of phosphorus sulfide, sulfur halide, elemental sulfur and alkali polysulfide at a temperature of between about 150 and about 170 0., and thereafter neutralizing said reaction product to form the salt.

20. A composition consisting of the reaction product obtained by first reacting an unsaturated cyclic ketone having at least 12 carbon atoms with hydrogen sulfide-ammonium hydrosulfide at between about room temperature and about 100 C., treating the resulting reaction product with phosphorus pentasulfide at a temperature of between about 150 and about 170 C. and neutralizing said reaction product with an alkaline earth metal.

DAVID E. ADELSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,266,325 Lazar et a1. Dec. 16, 1941 2,353,491 Oberright July 11, 1944 2,361,805 Wilson Oct. 31, 1944 2,383,497 Ott et al Aug. 28, 1945 2,413,648 Otto Dec. 31, 1946 2,419,153 Musselman et al. Apr. 15, 1947 Certificate of Correction Patent N 0. 2,489,249 November 29, 1949 DAVID E. ADELSON It is hereby certified that error appears in the printed specification of the above oz numbered patent requlring correction as follows:

Column 16, line .5, for 130 read 150;

and that the said Letters Patent should be read with this correction thereinythat the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 9th day of May, A. D. 1950.

[sun] THOMAS F. MURPHY,

Assistant C'ommz'egz'oner of Patents. 

